Compound of the anthraquinone series and process of making same.



Processes forPreperi UNITED smrns PATENT OFFICE.

ROLAND HEINRICH SGHOLL, OF KARLSRUHE, GERMANY, ASSXGNOR TO BADISCHE'ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-GN-THE' RHINE, GERMANY, A CGRPORATION.

COMPOUND 05 THE ANTHRAQUINONE SERES AND PROCESS OF MAKING SAME.

He. seems.

Specifiestion of Letters Patent.

Patented Aug. 1;, 1900.

Applination flied Fain-ear; 3,1986. E u'laI No. 299,276:

To all whom it may concern.- 7 7' Be it known that I, ROLAND Hnmnron 301101.14, rofessor of ehemistryend doctor of gllilosop y, a. subject of the Grand Duke of den, residing at Karlsruhe, in the Grand Duchy of Baden, German Empire, have invented new and useful Improvements in new Compounds of the Anthrequinone Series and the Some, of which the foiiowing is a epeei motion. My invention relates to the production of new oompounds of the enthrequinone series,

I have discovered that by heating halogen anthrequinones with a metal, such as copper, which has the power of Withdrawing halo on, I am enabled to obtain compounds in W iioh two anthmquinone residues are joined together. To these new compounds I have given the name dienthrequinonyl" C0111- pounds, and they are valuable starting matev rials for the production of coloring-matters.

For instance, by condensing their halo en derivotives with aromatic amins and en foneting the eondensetion rod nets coloringmatters can be obtaine which dye wool red The new compounds which I desire to claim enerieaily possess a greenislnyollow to yet fiJWi'h-blOWn color, are orystnliizeble from xylene, and are soluble in nitrobenzeno and in enilin. They are also soluble in noncontreted suifiuie a(:id, vie1ding brown-yellow tn ellow solutions. The new compound, which {desire to claim specifically, is zz dimethyh 1 .1-diantin'aquinonyl, which mm he obtained by heating l-halogen-Z- moLli 'imam-re ninone withcopper-powder, and can in, reorys tnliization from xylene be olitainwi in yoiiowisl'i-hrown prisms, wiiirli' yiold a yoliow solution in oi'uwontmtml sulfuric acid The i'ollowin I exmnpies wili serve to furtheriiiustmte t in nature of my invention and the method of r-ziirry'ing it into Wait-tine} eifec-lt; but the invention is not confined to these examples. The parts afe by weight,

Exempio i: Grind weli together ten (i9) parts of i-iodii-Z-iIiethylenthrequinone and eight (8) ports of copper-powder, and then beat the mixture in a motel bath at a torn pereture of about two hundred and ten (210) do nos eentigrede. The iodin comund me L5, and writer a. short time reaction takes piece, yellow fumes being evolved, end

' (278) degrees eentigrede.

the temperature of the mixture rises to about two hundred and ninety (290) de ees centigrede} the mixture becoming liar As soon as the to wpereture begins to fall a ply hoot and maintain for about fifteen glia minutes a temperature of two hundred e'nd sevent Ailow the med to cool and then grind it and, if necessary, further heat'fer ten {10) minutes at a temnereture of two hundred and seventy (270) do grees oentigiede; In order tofreetlie formed 2.2'-djmet yl-il' dienthre'quinenyl from eopper iodid and unaitered copper, treat the powdered reaction mixture for from one {1) to two {2) hours with dilute nitric acidnt'e' temperature of about fifty (50) degrees eon tigrede, filter of? and wash with warm weter and dry. The new compound can be recrystallized from xylene and obtained in the form of yelloe'ish brown prisms, which are eosiiy soluble in boiling nitrobenzene and in boiling eneiin. They are also soluble in oozieentinted sulfuric acid, yielding a yeliow solution.

' Example 3: 'Mix well together ten (10) parts oi 1-brow-241iethylanthrequinone and eight {8) parts of co per-powder and heat the wiioie in a motel lmth at a. temperature of twohundrod end sixiy(260) degrees centigrmlo. After about half an hour {30miniiteis) the temperature begins to lower, whereupon heat for another fifteen minutes to n temperature of two hundred and seventy five (235) degrees eenti ode. Aiiow the melt to cool, owder it fine y, and then di est the powdorei melt with dihitn nitrie aoit for half on hour (30 minutes) at a temperature of about fifty (56) degrees oentigmdo. Filter oil and wash with Warm water and dry. The 3.2-dimotl=.yi-1 .1dienthroquinonyi formed can be purified by boiling with xylene and then eviqmrnting to dryness the solution ohmined Example 3: Heat together in a metal bet-h at a temperature of two hundred and sixty (260) degrees eenti mde ten (10) ports 01' l-QlliiW g-1ii 3iiifl-RHITlTILiUlDOIIO and eight (8) ports of supper-pow or. The temperature oi" the mess rapidly rises to about two hundred and ninety i290") degrees centigmde, end after from twenty to minutes begins to lower At this po nt apply external heat and maintain the melt for about fifteen S15) minutes at atemperature of two hunrred and eighty (280) degrees centigrade. Allow the melt to cool, powder it finely, and treat it with dilute ni trio acid, as described in the foregoing Examle 2, in order to free it' from cop er-powder,

he 2.2 dimethyl 1.1 diant aquinonyl thus obtained. may be purified by treatment with xylene in the manner described in the foregoing Exam ie 2.

Example 4: '2: well to ether four (4) parts of 1-iodo-2-methylantfira uinone and five (5) parts of finely-divided si var-powder and heat the whole in a metal bath at a temperature of from two hundred and sixty (260) degrees centigrade to two hundred and seventy-five(275) degrees centigrade and maintain the melt for about forty-five minutes at this tem erature. Allow the melt to cool, powder it nely, and heat again for thirty (30) minutes at the same tern erature. After the melt has cooied pow or it very finely and extract the 2.2-dimethyl-1.1-

dianthraquinonyl formed by means of hot xylene.

Example 5: Heat to ether ten (10) parts of 4 -iodo l .3-diamethy anthraquinone (ob- Fined from 1.IQ-dimethytanthraquinone by nitration, reduction, and exchanging the amide group for iodin) and ei ht (8) parts of copper-powder in a metal bat at a temperature of two hundred and ten (210) de 'ees centigrade, the mass becomes fluid an the temperature risesrapidly to two hundred and forty-five (245) degrees oentigrade, and then fails a ain and the reaction products solidifies. I he crude product can be extracted with benzene and the solution obtained concentrated. Upon recrystallization from benzone the new compound is obtained in yellow crystals.

Now what I claim is- 1 Theprocessfor the reduction of anthrauinone compounds by eating a halogen ant roquinone with a metal which has the power of withdrawing halogen.

2. The process for the roduction of anthrauinone compounds by eatin a halogen an t raq i inone with copper-powr er.

3. he process for the production of 2.2 dimethyl-l.1-dianthrar uincnyi by heating 1-halogen-Z-methyl-ant iraquinone with copper-powder.

4. As new articles of manufacture the anthraquinone compounds which can be obtained by heating a halogen anthraquinone with a metal which has the power of with drawini halogen, which com ounds possess a greenis -yellow to ellowishrowncolor, and which are recrysta lizable from xylene and are soluble in nitrobenzene and in anilin and are also soluble in concentrated sulfuric acid yielding brown-yellow to yellow solutions.

5. As a new article of manufacture 2.2; din'iethyl-l.1-dianthraquinonyl which can be obtained by heating I-haIogen-Z-meth anthraquinone with copper-powder, and which. can by recrystallization from xylene be obtained in yellowish-brown prisins,which are soluble in nitrobenzene and in anilin and also in sulfuric acid yielding a yellow solution In testimony whereof I have hereunto set my hand in. the presence of two subscribing witnesses.

ROLAND HEINRICH SCHOLL' Wi t nesses J. Acne. LLorn, Jos. H. Laura. 

